CN115247269B - Integrated photo-anode device, battery, preparation method and application thereof - Google Patents
Integrated photo-anode device, battery, preparation method and application thereof Download PDFInfo
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- CN115247269B CN115247269B CN202210530172.4A CN202210530172A CN115247269B CN 115247269 B CN115247269 B CN 115247269B CN 202210530172 A CN202210530172 A CN 202210530172A CN 115247269 B CN115247269 B CN 115247269B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 43
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000005751 Copper oxide Substances 0.000 claims abstract description 26
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 26
- 239000011889 copper foil Substances 0.000 claims abstract description 24
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 18
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 229910000807 Ga alloy Inorganic materials 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 32
- 210000004027 cell Anatomy 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 239000002070 nanowire Substances 0.000 claims description 12
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 11
- 239000005750 Copper hydroxide Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 10
- 210000001787 dendrite Anatomy 0.000 claims description 9
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical group [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 38
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/087—Photocatalytic compound
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C25B3/00—Electrolytic production of organic compounds
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Abstract
The invention belongs to the technical field of photoelectrocatalysis materials, and relates to an integrated photo-anode device, a battery, a preparation method and application thereof. The preparation method of the integrated photo-anode device comprises the following steps: immersing copper foil in potassium hydroxide solution for anodic oxidation, and then placing the copper foil into potassium hydroxide solution containing methanol for positive potential cyclic voltammetry treatment to prepare a copper oxide nano-sheet array; coating indium-gallium alloy on the golden edge of the solar cell illuminating surface, and then bonding a copper foil on the golden edge; bonding the copper oxide nano sheet array on the back surface of the solar cell by adopting indium-gallium alloy; sealing the periphery of the solar cell to obtain the solar cell.
Description
Technical Field
The invention belongs to the technical field of photoelectrocatalysis materials, and relates to an integrated photo-anode device, a battery, a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
In order to relieve the growing greenhouse effect, realize the global carbon neutralization, develop the way of reducing the carbon dioxide into the value-added chemicals with high efficiency, have important significance to scientific research and practical application. At present, a high-efficiency photovoltaic device is properly coupled with an electrochemical cell, and related researches on reduction of carbon dioxide into value-added chemicals by photoelectrocatalysis are carried out, wherein in a carbon dioxide reduction electrolytic cell, the energy utilization efficiency of a ferronickel-based electrocatalyst commonly used in an anodic oxygen production reaction is low, and anode corrosion is easy to occur, so that the stability of a cathode is reduced. In addition, the reaction rate is low, the stability is poor, and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an integrated photo-anode device, a battery, a preparation method and application thereof.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing an integrated photoanode device, comprising the steps of:
Immersing copper foil in potassium hydroxide solution for anodic oxidation, and then placing the copper foil into potassium hydroxide solution containing methanol for positive potential cyclic voltammetry treatment to prepare a copper oxide nano-sheet array;
Coating indium-gallium alloy on the golden edge of the solar cell illuminating surface, and then bonding a copper foil on the golden edge;
Bonding the copper oxide nano sheet array on the back surface of the solar cell by adopting indium-gallium alloy;
Sealing the periphery of the solar cell to obtain the solar cell.
In a second aspect, the present invention provides an integrated photoanode device, prepared by the preparation method.
In a third aspect, the present invention provides an integrated battery comprising an anode, a cathode and an electrolyte, wherein the anode is the integrated photo-anode device, the cathode comprises a carrier and copper nano dendrites adhered to the carrier, and the anode and the cathode are connected by wires;
The preparation method of the copper nano dendrite comprises the following steps: and (3) carrying out anodic oxidation on the copper foil in potassium hydroxide solution, and then carrying out negative potential cyclic voltammetry treatment in potassium salt solution to obtain the copper foil.
In a fourth aspect, the present invention provides the use of said integrated photoanode device or said integrated battery for the photoelectrocatalytic reduction of carbon dioxide to formate.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
The coupling of the photovoltaic cell phosphorus indium gallium/gallium arsenide/germanium and the anode catalyst copper oxide nano-sheet array constructs an electrochemical cell with in-situ self-selectivity copper cathode and photovoltaic-copper oxide photo-anode, and cathode poisoning can be effectively avoided, so that excellent stability is maintained.
The invention can obtain the cathode catalyst copper nano dendrite and the anode catalyst copper oxide nano sheet array through simple anodic oxidation and in-situ pre-reduction. An integrated photo-anode device for coupling the photovoltaic cell phosphorus indium gallium/gallium arsenide/germanium with the anode catalyst copper oxide nano-sheet array is constructed by using indium gallium alloy and epoxy resin. Has higher formic acid production rate than the same kind of photoelectrocatalysis carbon dioxide reduction. The conversion efficiency of solar energy into formate was 3.63% over a period of 12 hours, and the formate production rate was 0.194mmol/h/cm 2.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is XRD of the cathode catalyst (Cu-1) and anode catalyst (CuO) prepared in example 1 and the cathode catalyst prepared in example 2 (Cu-2) and example 3 (Cu-3).
FIG. 2 is a Scanning Electron Microscope (SEM) of the cathode catalyst (Cu-1) and anode catalyst (CuO) prepared in example 1 and the cathode catalyst prepared in example 2 (Cu-2) and example 3 (Cu-2).
Fig. 3 is an efficiency graph of the cathode catalyst and the anode catalyst prepared in example 1.
Fig. 4 is an efficiency graph of the battery prepared in example 1.
Fig. 5 is a stability diagram of the battery prepared in example 1.
Fig. 6 is a schematic view of the battery prepared in example 1.
The structure of the cell can be seen in fig. 6, in which the anode performs a reaction of oxidizing methanol to formic acid under sunlight, and the cathode performs a reaction of reducing carbon dioxide to formic acid.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the present invention provides a method for preparing an integrated photoanode device, comprising the steps of:
Immersing copper foil in potassium hydroxide solution for anodic oxidation, and then placing the copper foil into potassium hydroxide solution containing methanol for positive potential cyclic voltammetry treatment to prepare a copper oxide nano-sheet array;
Coating indium-gallium alloy on the golden edge of the solar cell illuminating surface, and then bonding a copper foil on the golden edge;
Bonding the copper oxide nano sheet array on the back surface of the solar cell by adopting indium-gallium alloy;
Sealing the periphery of the solar cell to obtain the solar cell.
The light-emitting surface of the solar cell generates current, and the current is conducted to the copper foil from the gold edge and then reaches the electrode to perform catalytic reaction.
Anodic oxidation is carried out on the copper foil to generate a copper hydroxide nanowire array, potassium hydroxide containing methanol is used as electrolyte, and the following reaction is carried out to generate a copper oxide nanowire array:
Cu(OH)2+OH--e-→CuOOH+H2O (4)
4CuOOH+CH3OH+OH-→4CuO+HCOO-+4H2O (5)
The photovoltaic cell phosphorus indium gallium/gallium arsenide/germanium is a commercial solar cell and is beneficial to large-scale application. The short-circuit current under simulated solar irradiation (AM 1.5G,100mW/cm 2) was 10.8mA/cm 2, the open-circuit voltage was 2.48V, and the fill factor was 80%.
When the content of the generated copper hydroxide nanowire array reaches the maximum, oxygen production reaction is started, the anodic oxidation voltage at the moment changes at the speed of 0.12V vs. RHE/s, and the taking-out is stopped immediately.
Preferably, the anodic oxidation has a current density of 8-12mA/cm 2;
The concentration of the anodized potassium hydroxide is 4-6mol/L.
In some embodiments, the positive potential cyclic voltammetry is completely converted to copper oxide nanoplatelets after the current density remains stable, at which point the removal is stopped.
The positive potential cyclic voltammetry ranges from 1.2 to 1.8V vs RHE.
Preferably, the concentration of potassium hydroxide in positive potential cyclic voltammetry is 0.8-1.2mol/L, and the concentration of methanol is 0.8-1.2mmol/L.
In a second aspect, the present invention provides an integrated photoanode device, prepared by the preparation method.
In a third aspect, the present invention provides an integrated battery comprising an anode, a cathode and an electrolyte, wherein the anode is the integrated photo-anode device, the cathode comprises a carrier and copper nano dendrites adhered to the carrier, and the anode and the cathode are connected by wires;
The preparation method of the copper nano dendrite comprises the following steps: and (3) carrying out anodic oxidation on the copper foil in potassium hydroxide solution, and then carrying out negative potential cyclic voltammetry treatment in potassium salt solution to obtain the copper foil.
In some embodiments, the anodized potassium hydroxide has a concentration of 4-6mol/L.
In some embodiments, the potassium salt is potassium bicarbonate, and the concentration of potassium salt is 0.4 to 0.6 mol/L.
Preferably, when carbon dioxide is used as a reactant, the method further comprises the step of introducing carbon dioxide into the potassium salt solution for half an hour.
In some embodiments, the negative potential cyclic voltammetry ranges from-0.4V to-1.2V vs RHE.
In a fourth aspect, the present invention provides the use of said integrated photoanode device or said integrated battery for the photoelectrocatalytic reduction of carbon dioxide to formate.
Proper coupling of the gallium indium phosphide/gallium arsenide/germanium with the anode catalyst copper oxide nanoplatelet array enables highly stable and efficient formate preparation from solar energy. Simultaneously, the cathode stably reduces carbon dioxide to formic acid, thereby realizing the high-efficiency production of formate with high added value by the cathode and the anode, greatly improving the yield of formate and reducing the burden of downstream purification/separation. In addition, an electrochemical cell with an in-situ self-selective copper cathode and a photovoltaic-copper oxide photo-anode is constructed, which can effectively avoid cathode poisoning, thereby maintaining excellent stability.
The invention is further illustrated below with reference to examples.
Example 1
The preparation method of the anode catalyst-copper oxide nano sheet array comprises the following steps:
(1) 16.8g of potassium hydroxide is dissolved in 60 ml of water, copper foil is put into the solution, and anodic oxidation is carried out on the copper foil until the voltage value is rapidly increased at the current density of 10mA/cm 2, and the growth of the copper hydroxide nanowire is stopped at the moment;
(2) 2.72g of potassium hydroxide was dissolved in 85 ml of water, 3.44. Mu.l of methanol was added thereto, and the copper hydroxide nanowires were put into the solution to conduct positive potential cyclic voltammetry (from 1.2V to 1.8V vs RHE). After the current density is stable and unchanged, the copper hydroxide nanowire array is completely converted into a copper oxide nanowire array.
The preparation method of the cathode catalyst-copper nano dendrite comprises the following steps:
(1) 16.8g of potassium hydroxide was dissolved in 60 ml of water, and the copper foil was placed in the solution and anodized at a current density of 10mA/cm 2 until the voltage value increased rapidly. At this time, the growth of the copper hydroxide nanowire is terminated
(2) 4.25G of potassium bicarbonate was dissolved in 85 ml of water and CO 2 was introduced for half an hour. The copper hydroxide nanowires described above were put into solution for cyclic voltammetry (from-0.4V to-1.2V vs RHE). After the current density is stable and unchanged, the copper hydroxide nanowire array is completely converted into copper-copper nano dendrites.
The preparation method of the integrated photo-anode device coupling the photovoltaic cell and the copper oxide nano-sheet array catalyst comprises the following steps:
1) And (3) coating the indium-gallium alloy on the gold edge of the illumination surface of the solar cell, then placing copper foil, bonding by using copper adhesive, and finally sealing the periphery of the solar cell by using epoxy resin to prevent water from entering.
2) Indium gallium alloy is also used to bond the anode catalyst copper oxide nanoplatelet array on the back side of the solar cell, and then epoxy is used to seal the periphery of the solar cell.
Example 2
Unlike example 1, argon was introduced for half an hour in step (2) in the preparation of the cathode catalyst, and the product obtained was designated as Cu-2.
Example 3
Unlike example 1, 3.57g of sodium hydrogencarbonate was added in step (2) to dissolve in 85 ml of water in the preparation of the cathode catalyst, and the obtained product was designated as Cu-3.
Electrocatalytic carbon dioxide reduction test:
CO 2 was introduced into a 0.5mol/L potassium bicarbonate solution for half an hour, and copper nanodendrites (cathode catalyst) were put into the solution for testing.
Electrochemical carbon dioxide reduction experiments were performed in a closed H-type reactor. The CO 2 reduction performance of copper nanodendrite materials of size 1 x 1cm 2 was tested. The gas phase reaction product was determined by Gas Chromatography (GC) and the liquid phase reaction product was determined by liquid phase nuclear magnetic hydrogen spectroscopy (NMR).
Electrocatalytic methanol oxidation to formic acid test:
1mmol/L methanol is added into 1mol/L potassium hydroxide solution, and a copper oxide nano-sheet array (anode catalyst) and an integrated photo-anode device (coupling between a photovoltaic cell and the copper oxide nano-sheet array catalyst) are placed into the solution for testing.
Experiments for generating formic acid by oxidizing methanol are carried out in an H-type reactor, and the methanol oxidation performance of the copper oxide nano-sheet array material with the size of 1X 1cm 2 is tested. The liquid phase reaction product was determined by liquid phase nuclear magnetic hydrogen spectroscopy (NMR).
Test results:
XRD of the cathode catalyst and anode catalyst prepared in example 1 and the cathode catalysts prepared in example 2 and example 3 are shown in fig. 1. It can be seen that the anode catalyst prepared in example 1 was a copper oxide nanoplatelet array and the cathode catalyst prepared was copper nanodendrites. The cathode catalyst prepared in example 2 was a copper nano-beam material, and the cathode catalyst prepared in example 3 was copper nano-particles.
The cathode catalyst and anode catalyst prepared in example 1 and the cathode catalysts prepared in example 2 and example 3 are shown in fig. 2 by Scanning Electron Microscopy (SEM). The anode catalyst prepared in example 1 showed a nano-plate array structure, and the cathode catalyst showed a nano-dendrite morphology. The cathode catalyst prepared in example 2 was a copper nano-beam material, and the cathode catalyst prepared in example 3 was copper nano-particles.
The efficiencies of the cathode catalyst and the anode catalyst prepared in example 1 are shown in fig. 3, and it can be seen that the anode catalyst can maintain >50% selectivity between-0.7 and-1.2 v vs. rhe and can maintain 63% of the highest selectivity at-1.1 v vs. rhe. It can be seen that the cathode catalyst maintains a selectivity of more than 90% between 1.33 and 1.58V vs. rhe, which can reach 94% at 1.45V vs. rhe.
The efficiency of the cell prepared in example 1 is shown in FIG. 4, and the selectivity of the anode and cathode is 88% and 58% respectively at an operating voltage of 2.18V and a current density of 10.08mA/cm 2.
The stability of the battery prepared in example 1 is shown in fig. 5, and it is understood that the battery can be maintained stable for 12 hours.
The structure of the cell can be seen in fig. 6, in which the anode performs a reaction of oxidizing methanol to formic acid under sunlight, and the cathode performs a reaction of reducing carbon dioxide to formic acid.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the integrated photo-anode device is characterized by comprising the following steps of: the method comprises the following steps:
Immersing copper foil in potassium hydroxide solution for anodic oxidation, and then placing the copper foil into potassium hydroxide solution containing methanol for positive potential cyclic voltammetry treatment to prepare a copper oxide nano-sheet array;
Coating indium-gallium alloy on the golden edge of the solar cell illuminating surface, and then bonding a copper foil on the golden edge;
Bonding the copper oxide nano sheet array on the back surface of the solar cell by adopting indium-gallium alloy;
Sealing the periphery of the solar cell to obtain the solar cell;
when the content of the generated copper hydroxide nanowire array reaches the maximum, oxygen production reaction is started, the anodic oxidation voltage at the moment changes at the speed of 0.12V vs. RHE/s, and the taking out is stopped immediately;
the anodic oxidation current density is 8-12mA/cm 2;
the concentration of the anodized potassium hydroxide is 4-6mol/L;
after the current density of the positive potential cyclic voltammetry is kept stable, the copper hydroxide nanowire array is completely converted into copper oxide nanosheets, and then the copper oxide nanosheets are taken out;
the range of positive potential cyclic voltammetry is 1.2-1.8V vs RHE;
The concentration of potassium hydroxide of positive potential cyclic voltammetry is 0.8-1.2mol/L, and the concentration of methanol is 0.8-1.2mmol/L.
2. An integrated photoanode device, characterized in that: prepared by the preparation method of claim 1.
3. An integrated battery, characterized in that: the integrated photo-anode device comprises an anode, a cathode and electrolyte, wherein the anode is the integrated photo-anode device of claim 2, the cathode comprises a carrier and copper nano dendrites adhered to the carrier, and the anode and the cathode are connected through wires;
The preparation method of the copper nano dendrite comprises the following steps: and (3) carrying out anodic oxidation on the copper foil in potassium hydroxide solution, and then carrying out negative potential cyclic voltammetry treatment in potassium salt solution to obtain the copper foil.
4. The integrated battery of claim 3, wherein: the concentration of the anodized potassium hydroxide is 4-6mol/L.
5. The integrated battery of claim 3, wherein: the potassium salt is potassium bicarbonate, and the concentration of the potassium salt is 0.4-0.6mol/L.
6. The integrated battery of claim 3, wherein: when carbon dioxide is used as a reactant, the method further comprises the step of introducing carbon dioxide into the potassium salt solution for a set time.
7. The integrated battery of claim 3, wherein: the range of the negative potential cyclic voltammetry is-0.4V to-1.2V vs RHE.
8. Use of an integrated photoanode device or the integrated battery according to claim 2 or any of claims 3 to 7 for the photoelectrocatalytic reduction of carbon dioxide to formate.
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| WO2015170987A1 (en) * | 2014-05-09 | 2015-11-12 | Universiteit Leiden | Process for forming a leaf-shaped nanoparticulate material, an electrochemical cell and a process to convert water |
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| WO2022064414A1 (en) * | 2020-09-25 | 2022-03-31 | Eni S.P.A. | Electrodes containing copper and copper oxides and preparation process thereof |
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| WO2015170987A1 (en) * | 2014-05-09 | 2015-11-12 | Universiteit Leiden | Process for forming a leaf-shaped nanoparticulate material, an electrochemical cell and a process to convert water |
| KR101858933B1 (en) * | 2017-12-29 | 2018-05-17 | 서울대학교산학협력단 | Heterogeneous metal nanowire electrode and preparing method thereof |
| WO2022064414A1 (en) * | 2020-09-25 | 2022-03-31 | Eni S.P.A. | Electrodes containing copper and copper oxides and preparation process thereof |
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